Sulfur-vulcanizable interpolymers comprising at least on ealpha-olefin and a polyvinylcycloalkane and a process for preparation



United States Patent Office Patented Dec. 7, 1965 3,222,331 SULFUR-VULCANIZABLE INTERPOLYMERS COM- PRISING AT LEAST QNE ALPHA-OLEFIN AND A POLYVINYLCYCLOALKANE AND A PROCESS FOR PREPARATION i i Edward W. Duck and Rinke Berl renboscli, both. of Amsterdam, Netherlands, assignorsto Shell Oil Company, New York, N.Y., a' corporation of Delaware N Drawing. Filed Apr. 25, 1962, Ser. No. 189,961 Claims priority, application Netherlands, July 26, 1961, 267,544 8 Claims. (Cl. 260-805) This invention relates to the copolymerization of alpha olefins with polyvinyl cycloalkanes. More particularly, it relates to the preparation of sulfur-vulcanizable copolymers.

' Copolymerization in which one or more alpha-monoolefins, e.g., ethylene or propylene, are used may be carried out with catalysts of the Ziegler of Natta types. However, products composed entirely of alpha-olefin units are substantially saturated and therefore are not readily subject to vulcanization except by the use of peroxides. The use of the latter entails certain technical and economic disadvantages: they are expensive and the products so derived have objectional odors.

'Means have been investigated for the copolymerization with alpha olefins of certain open chain diolefins.

It is an object of the present invention to improve the process for the polymerization of alpha olefins. It is another object of this invention to provide a process for the preparation of sulfur vulcanizable alpha olefins. It is a particular object of the invention to provide not only the process for preparation but the sulfur vulcanizable polymers per se. Other objects will become apparent during the following detailed description of the invention.

Now, in accordance with the present invention, sulfur vulcanizable copolymers of alpha olefins comprise those in which from about 1 to about 30 mol percent of the bound monomers in the copolymers are polyvinyl mono: cycloalkanes, the copolymers having 2-25 double bonds per 1,000 carbon atoms. Still in accordance with the present invention, a process is provided whereby an alpha olefin having from two to eighteen carbon atoms per molecule and being an unsaturated straight chain monoolefin is copolymerized in the presence of a polymerization catalyst with a polyvinyl substituted cycloalkane to produce the new copolymers of the invention. More particularly, such copolymers are preferably polymerized in the presence of catalysts of the Ziegler or Natta type.

Suitable alpha monoolefins are for example, ethylene, propylene, butene-l, styrene, hexene-l, octene-l and mixtures thereof. Preferably, the mono alpha olefins have from 2 to 6 carbon atoms each and still more preferably mixtures of ethylene with either propylene or butene-l are employed. In order to provide a sulfur vulcanizable copoly-mer, the above-described unsaturated straight chain monoolefins are copolymerized with polyvinyl cycloalkanes. These may be either monocyclic or polycyclic, although the monocyclic are preferred. Typical polyvinyl monocyclic alkanes are as follows:

1,2-divinyl cyclohexane 1,3-divinyl cyclohexane 1,4-divinyl cyclohexane 1,2-divinyl cyclopentane 1,3-divinyl cyclopentane l,Z-divinyl-4-methyl-cyclohexane 1 ,4-divinyl-2-methyl-cyclohexane 1,2,4-trivinyl cyclohexane 1,3,5-trivinyl cyclohexane 1,2,3-trivinyl cyclohexane 1,2,4-trivinyl cyclopentane 1,2,5-trivinyl cyclopentane l,2,4-trivinyl-5-methyl-cyclohexane 1,2,5-trivinyl-4-methyl-cyclohexane In addition to or in place of the vinyl substituted monocycloalkanes, polyvinyl polycycloalkanes may be utilized. These are usually mixed di or trivinyl substituted polycycloalkanes, the mixtures usually comprising isomers derived by a simple vinyl substituting mechanism. Typical polycycloalkanes from which mixed di or trivinyl substituted alkanes may be derived are as follows:

Carane Pinane Camphane Decalin Perhydrophenanthrene Cholane While the amount of vinyl substituted cycloalkanes may vary from about 1 to about 30 mol percent of the bound monomers in the coplymers formed according to the present invention, it is preferred that they constitute between about 2 and about 10 mol percent of the average copolymers. Particularly suitable vinylcycloalkanes may be obtained by heating cyclododecatriene (1,5,9) to a temperature between 300 and 650 C. and separating the lower boiling reaction product from the starting material by distillation.

The copolymers of the present invention may be prepared by the use of catalysts generally known as coordination catalysts. These are made from components of two types; component A comprises compounds of the transition heavy metals of groups IV, V, and VI beginning with titanium, vanadium and chromium and component B comprises organometallic compounds and hydrides of groups I, II, and III of the Periodic System. The compounds of component A are preferably halides, oxy halides, and alcoholates, the preferred metals being titanium and vanadium. The metals of component B are preferably lithium, sodium, magnesium and aluminum and the organic portions are preferably alkyl radicals. In these organo metallic compounds, the valenoes of the metal may be partially satisfied by halogen or alkoxyl, provided of course that at least one bond connects the metal with an organic radical. Mixtures of two or more compounds of the types described above may often be used to an advantage. These catalysts per se are not the subject of the present invention.

As is well known, these catalysts must be used in the virtual absence of oxygen, Water or other materials with which they react, and for this reason solvents in which they are generally used are greatly limited, the preferred one being the saturated aliphatic and hydroaromatic hydrocarbons and certain non-reactive halogen compounds such as tetrachloroethylene and chlorobenzene. These solvents conveniently serve as solvents for the polymerization of the olefins which for example is usually carried out in the dilute suspension of the catalyst.

The polymerization normally will be carried out at ordinary temperatures and pressures although it is usually convenient to allow the temperature to rise spontaneously to from 50 to 60 C. due to the heat of the reaction. The rate of the reaction may be increased by the use, of increased pressures, e.g., up to 1000 atmospheres or above, or by increased temperatures up to about 0., although itis to be understood that elevated temperatures and pressures are not required. When found desirable, the polymerization may be carried out at lower temperatures and pressures.

Catalysts suitable for the present process can be obtained, for instance, by using any one of the following combinations of catalyst-forming components.

(a) A vanadium oxyhalide, for instance, VOCl or VOCI together with a compound of the type AlR 4i The following examples illustrate the preparation and vulcanization of the subject copolymers.

Example I (halogen) in which R stands for a hydrocarbon radi- Some copolymerization experiments were carried out cal and n is 1-3 for instance an alkylaluminum sesquiusing as the monomers ethene, propene and a mixture halide, such as Al isobutylsesquichloride. of 1,2,4- and 1,3,5-trivinyl cyclohexane (TVCH) ob- (b) A vanadium trihalide, for instance VCl together tained by heating cyclododecatriene-(1,5,9) to about with a compound of the type AlR (halogen) or AlR in 450 C. and separating the lower-boiling reaction prodwhich the symbols R represent equal or different hydro- 10 net from the base material by distillation and purified by carbon radicals, for instance, Al(C H Cl. treatment with Al(C H and percolation over A10 (c) Titanium trihalide, for instance TiCl together The copolymerizations were effected in the diluents listed with a compound of the type AlR (OR) or AlR in which in Table I and with the aid of VOCl and ethylaluminum the symbols R again stand for equal or different hydrosesquichloride as the catalyst-forming components. carbon radicals, for instance, Al(C H (OC H In all the experiments the TVCH was added to a con- Preferably, combinations (a) or (b) are applied. centrated solution of VOCl in the. diluent, after which Insofar as a trialkyl compound is used as the catalystthe solution was diluted with the same diluent. Then, forming compound in the combinations mentioned above consecutively, while the mixture was thoroughly stirred, ((a)(c), incl.), the aluminum trialkyls which contain the temperature was raised to 60 C., a gaseous feed more than 5 carbon atoms, for instance aluminum triconsisting of 30% m. of ethene and 70% m. of propene, n.hexyl or aluminum tri-n.decyl, are preferred. was passed through and a concentrated solution of ethyl- In all the above-mentioned types of aluminum comaluminum sesquichloride in the diluent was admixed. pounds R can represent, besides an alkyl group, a cyclo- The total amount of diluent used was invariably 300 alkyl group or an aromatic radical. milliliters. The amounts of catalyst-forming component As the diluent in the process according to the invention used for the polymerizations were, per liter of diluent, the usual types may be used, both aliphatic and aromatic 10 millimoles of VOCl and 20 millimoles of Al(C H hydrocarbons, as well as chlorinated hydrocarbons, for 1 Cl The copolymerizations started at once when instance isooctane, benzene and tetrachloroethane. the ethylaluminum sesquichloride was admixed. The

It is a preferred practice to mix the polyvinyl cyclorate of throughput of the ethene/propene mixture was adalkane with one of the catalyst components prior to justed in such a manner that the exit gas amounted to admixture with the remaining catalyst component and about 30% v. of the feed. Under these conditions the the copolymerizable olefin monomer. copolymerizations were continued for one hour. Then The catalyst components should be employed in molar 5 to 10 ml. of a mixture of hydrochloric acid and ethanol ratios varying from about 1:10 and 10:1, preferably from was added to inactivate the catalyst. The contents of about 1:3 and 3:1. the reactor were subsequently poured into an equal Ordinarily, softer products are obtained from the oleamount of ethanol. After it had been separated, the fins having longer carbon chains and from vinyl subcopolymer was washed out with ethanol and dried in stituted cycloalkanes of higher molecular weight. It is vacuo under nitrogen at 60 C. The yields, composioften advantageous to employ two monoolefins, particutions and intrinsic viscosities (I.V.s) measured at 135 C. larly where they occur in mixtures normally or where in decalin of the copolymers thus obtained, are recorded particular properties are desired. For example, the mix in Table I. For comparison the results of a correspondture of ethylene and propylene (or butene-l) in amounts ing copolymerization without applying TVCH are also of about -80 mol percent of ethylene in the final polyincluded (experiment No. 1).

TABLE I v Copolymers Amount of Exp. Diluent CH, m1. Solubility Propene Number of No. per liter Yield, in cold content, double bonds of diluent gJliter I.V.- hexane, percent In. per 1,000 0. percent (infrared atoms (intraanalysis) red analysis) 0 25 4.1 29 39 0.1 10 30 3.7 81 46 2.7 25 26 3.1 72 41 4.9 do 50 30 2.4 52 36 11.0 Tetrachloroethane 25 36 1. 6 41 5. 1

mer is particularly useful in giving products with elas- Example 11 tomeric properties of the kind desired.

The monomers may be added gradually to the catalyst suspension or solution or they may all be added entirely at the start of the reaction. Alternatively, one or more may be added at the start and the balance may be added gradually throughout the polymerization. Additional catalysts may be injected during the reaction it found to be desirable. All of the processes including making the catalyst and isolating and purifying the product may be carried out batchwise or continuously.

The copolymers of the present invention may be milled and compounded satisfactorily in the same manner as milling and compounding of rubbers and the known synthetic elastomers, and may be cured with sulfur or sulfurtype vulcanizing agents in the same manner as rubber. As with rubber, the tensile properties are improved by incorporating carbon black and other compounding ingredients.

Example Ill Experiment No. 3 of Example I was repeated, with the difference that instead of the VOCl solution the reaction product obtained at C. from 5 millimoles per liter of VCL, annd 2.5 millimoles per liter of Al(C H Cl,

instead of 20 millimoles per liter of Al(C H 01 1/2 millimoles per liter of Al(C H Cl and instead of 300 milliliters of isooctane 500 milliliters of isooctane was used, and that the duration of polymerization was A2 hour instead of 1 hour. In this experiment a polymer yield of 36 g. per liter was obtained, the IV. of the copolymer being 4.0, its solubility in cold hexane 46% w., its propene content 46% m. and the number of double bonds per 1000 carton atoms 6.6.

Example IV TABLE II Vulcanization Results Copoly- Terpoly- 'lerpolymet 1 mar 3 met 4 Tensile strength, kg. /cm. 24 92 81 Elongation at rupture, percent. 899 669 581 300% modulus, kgJcm. 40 41 We claim as our invention:

1. 'Sulfur-vulcanizable unsaturated elastomeric random copolymers of at least one terminally unsaturated straight chain mono-olefin containing 2-6 carbon atoms per molecule and 25-10 mol percent of a trivinyl monocycloalkane, the cycloalkane ring having 5-6 carbon atoms in the .ring, the copolymers having 2-25 double bonds per 1,000 carbon atoms.

2. Sulfur-vulcanizable unsaturated elastomeric random copolymers of at least one terminally unsaturated straight chain mono-olefin containing 2-4 carbon atoms per molecule and 2.5 10 mol percent of a trivinyl monocyclohexane, the copolymers having 2-25 double bonds per 1,000 carbon atoms.

'3. Sulfur-vulcanizable unsaturated elastomeric random terpolymer of ethylene, propylene and 25-10 mol percent of a trivinyl monocyclohexane, the terpolymer having 2-25 double bonds per 1,000 carbon atoms.

4. A terpolymer according to claim 3 having an intrinsic viscosity of 0.5-5.0, a solubility in cold hexane of by weight, and 225 double bonds per 1000 carbon atoms.

5. The process of preparing a copolymer according to claim 1, in which a catalyst having components A and B is utilized, wherein the catalyst is selected'from the group consisting of:

Component A Component B A vanadium oxyhalide with an aluminum alkyl halide;

A vanadium trihalide with an aluminum alkyl halide;

A vanadium trihalide with an aluminum trialkyl;

A titanium trihalide with an aluminum alkyl alkoxide; and A titanium trihalide with an aluminum trialkyl,

the steps comprising:

( 1) admixing the trivinyl monocycloalkane with one of the catalyst components;

(2) thereafter mixing therewith the terminally unsaturated monoolefin and the second catalyst component;

(3) randomly copolymerizing the monomers in an inert medium;

(4) and isolating the copolymer from the inert medium.

6. A process according to claim 5 wherein the catalyst comprises a combination of a compound of a heavy transition metal of Groups 1V, V and VI of the Periodic Table and an organometallic compound B of Groups I, II and HI of the Periodic Table, said compounds being utilized in a molar ratio between 1:10 and 10: 1.

7. A process according to claim 6 wherein the trivinyl monocycloalkane is mixed with one of the catalyst compounds prior to admixture with the second catalyst compound and the mono-olefin.

8. A process according to claim 6 wherein the catalyst comprises a mixture of a vanadium oxyhalide and an aluminum alkyl halide.

References Cited by the Examiner UNITED STATES PATENTS 2,933,480 4/ 1960 Gresham et al 260-805 FOREIGN PATENTS 1,065,413 9/ 1959 Germany.

JOSEPH L. SCHOFER, Primary Examiner.

JOSEPH R, LIBERMAN, Examiner. 

1. SULFUR-VULCANIZABLE UNSATURATED ELASTOMERIC RANDOM COPOLYMERS OF AT LEAST ONE TERMINALLY UNSATURATED STRAIGHT CHAIN MONO-OLEFIN CONTAINING 2-6 CARBONATOMS PER MOLECULE AND 2.5-10 MOL PERCENT OF A TRIVINYL MONOCYCLOALKANE, THE CYCLOALKANE RING HAVING 5-6 CARBON ATOMS IN THE RING, THE COPOLYMERS HAVING 2-25 DOUBLE BONDS PER 1,000 CARBON ATOMS. 